English   español  
Por favor, use este identificador para citar o enlazar a este item: http://hdl.handle.net/10261/112049
Compartir / Impacto:
Estadísticas
Add this article to your Mendeley library MendeleyBASE
Ver citas en Google académico
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar otros formatos: Exportar EndNote (RIS)Exportar EndNote (RIS)Exportar EndNote (RIS)
Título

Boron functionalization of hydridotris(pyrazolyl)borate ligand on osmium complexes

Autor Bajo, Sonia ; Esteruelas, Miguel A. ; López, Ana M. ; Oñate, Enrique
Fecha de publicación 2014
Citación XXXII GEQO (2014)
Resumen[Work hypothesis and objective]: In most Tp-complexes (Tp=hydridotris(pyrazolyl)borate), the Tp ligand acts as an spectator that rarely undergoes transformations. As a part of our ongoing chemistry on Os-Tp complexes we report here the unexpected role of the B-H unit of the ligand, which acts as a claw-tail of the scorpionate to abstract an unsaturated group from the saturated metal center, allowing a subsequent reaction in another ligand. [Results]: The ethylene-pyridyl derivative OsTp{η1-C[NC5H3Me]}(η2-CH2=CH2)(PiPr3) reacts with two equivalents of phenylacetylene or 1,1-diphenyl-2-propyn-1-ol to give the corresponding alkynyl-vinylidene derivatives. Treatment of the hydroxyalkynyl-hydroxyvinylidene derivative with aluminium oxide promotes the dehydration of the hydroxyvinylidene to allenylidene and the subsequent isomerization of the hydroxyalkynyl ligand into an α,β-unsaturated acyl group. The B-H bond of the Tp ligand abstracts the allenylidene ligand from the metal center providing an allenyltris(pyrazolyl)borate ligand. As a result of the migration, the decarbonylation of the acyl group takes place to form the alkenyl-carbonyl derivative OsTpCH=C=CPh2(CH=CPh2)(CO)(PiPr3). The isomerization of the allenyl substituent of the borate ligand to alkynyl is promoted by a weak base as acetonitrile. These transformations represent very rare examples of boron functionalization of a Tp ligand.
Descripción Trabajo presentado a la XXXII Conference Expert Group Meeting on Organometallic Chemistry celebrada en Tarragona (España) del 17 al 19 de septiembre de 2014.
URI http://hdl.handle.net/10261/112049
Aparece en las colecciones: (ISQCH) Comunicaciones congresos
Ficheros en este ítem:
Fichero Descripción Tamaño Formato  
accesoRestringido.pdf15,38 kBAdobe PDFVista previa
Visualizar/Abrir
Mostrar el registro completo
 


NOTA: Los ítems de Digital.CSIC están protegidos por copyright, con todos los derechos reservados, a menos que se indique lo contrario.